Method of making novel products from whey



- terized by capacity Patented Mar. 29, 1949 UNITED STATES PATENT OFFICE 2,465,906 METHOD or MAKING NOVEL ritoDUo'rs FROM WHEY Reginald E. Meade and Pa asslgnors to ton, Wis

ul D. Clary,

Western Company, San Francisco, Calif., a corporation of California Application June 6, 1945, Serial No. 597,934

Claims.

This invention relates to methods of making novel products derived from whey and characfor being heat treated without the disadvantageous results normally flowing from the heat treatments conventionally carried out on whey and the like.

It is known that certain disadvantages and difliculties attend the heat treatment of liquid lacteal products such as whey. Such heat treatplete dehydration, such as concentration, spray drying or drum drying. More particularly, heat treatment of whey gives rise to a cooked or stale flavor and to a brown discoloration. On concentration of whey, a scaly deposit of calcium phostion of the lactose content of whey is lost during spray drying, as evidenced by an analytical determination of the lactose content of Whey prior to and after spray drying.

-We have now discovered that removal of a major portion of the mineral and acid content of whey together with certain other decomposition heat treatment or on subsequent storage. centration may be carried out without any grainy or sandy lactose particles. Such demineralized, deacidified whey may be spray dried to form a stable, relatively non-hygroscopic, palatable, easily dispersible, free flowing powdery product that does not turn brown on storage. The products of the methods 01' this invention contain substantially the whole lactose content of the starting material together the protein content of the original starting mateposition products of the starting material.

For the preparation of the novel compositions of the present invention we remove from whey a major portion of the mineral and acid (including amino acid) content. The reason for the reremoval of amino y from disclosures made hereinbelow.

More particularly, a liquid lacteal product such as whey is first contacted with a decationizing of the product has been effected, for instance, to a. 3.0% or smaller ash content. It the initial treatment with a decationizing medium is carthe pH value of the product to about 6.0 to 7.5, further treatment with such media is ordinarily not required. I

If desired, the whey may be alternately percolated through decationizing and deacidifying media, in repeated cycles, without bringing the pH down to the isoelectric point of the Whey protein, whereby precipitation of such protein is avoided.

It is therefore an important object of the present invention to prior to heat treatment or storage thereof.

.provide a novel type prising lactose as y and distinguished by excellent keeping qualities,

. f 'a'lactose content that sub tantial decomposition,

' and protein contents, and capacity of being more ori'less completely dehydrated to form relatively stable, palatable products.

' --.A further object ofv the present invention is to provide a whey concentrate relatively free Anotherobject of the present invention is to of liquid lacteal product comthe predominant ingredient has not been subjected to modified mineral, acid from discoloration and cooked or stale flavors due to sterilization or canning and capable of being stored without the formation of calcium phosphate deposits and without precipitation of grainy or sandy lactose particles, which concentrates can be spray dried to form palatable, free flowing, easily dispersible powdery products that also contain substantially the total lactose present in the starting material.

- Still another object of the present invention is to provide spray dried products derived from whey and having the properties mentioned in the preceding paragraphs.

Other and further objects and features of the present invention will become apparent to those skilled in the art from the following description drawings, and appended claims. I

Figures 1 to 4 of the drawings show in graphical form the percentage increase or decrease in weight of ordinary spray dried whey and or spray dried whey treated according to the present invention when exposed to four different atmospheres of various relative humidities for prolonged periods of time.

According to our'method ordinary whey obtained by rennet or acid treatment of cows milk, may be passed through a bed of or otherwise contacted with a decationizing medium capable of replacing metal ions with hydrogen ions, such as the d'ecationizing media disclosed in the article by Robert J. Myers et al., on pages 697-706, volume 33 (1941) of Industrial and Engineering Chemistry. The resinous decationizing media are particularly suitable. A preferred decationizing medium is Ionac-C," manufactured by American Cyanamide and Chemical Corporation. Preferably the rate of flow of the whey through the decationizing medium is so regulated that the efiiuent has a pH of 2.0 or less. The direction of flow is preferably upwardly through the medium, in order to disperse said medium and'thereby prevent entrapment of particulate matter.

After exhaustion, the decationizlng medium may be revivified by treatment with a dilute acid, for instance, dilute hydrochloric acid.

The decationized whey may then be passed through a bed of, or otherwise contacted by, a deacidifying medium capable of absorbing acids such as one of the deanionizing or, more properly, deacidifying absorbent media disclosed in the above identified article by Robert J. Myers et a1. Resinous deacidifying media are especially suitable. -A preferred material is Amberlite IR- i manufactured by Resinous Products and Chemical Company. Preferably th rate of flow of decationized whey through the deacidifying media'is regulated so that the eflluent has a 'pH value of from 6.0 to 7.5. The direction of flow should be upward through the medium, to flush away precipitatecf protein material into a zone of higher pH conditions where the protein is redissolved.

After exhaustion, the deacidifying medium may be revivifled by treatment with a dilute al- 1 kali solution, for instance, a dilute solution 0! sodium hydroxide.

It should be understood that similar results can be achievedby repeated cycles involving successive contacts with a decationizing medium and'a deacidiiying' medium, inwhich cycles the initial reduction of pH values is carried out only, for

example, to'a value of about 3.8. In other words, distributed between a plurality I thetreatment is of cycles, and the whey or other lactose containing material are not exposed to a very low pH.

The whey product obtained by thus percolating whey through a 'decationizing and deacidifying media has a total solids content of which only about 2.0% may be ash. The remainder of the total solids content consists principally of 86.5% lactose, and 11.5% non-casein protein. Much less ammonia is evolved in the treatment of demineralized, deacidified whey with calcium hydroxide than in the treatment of ordinary whey.

The modified whey obtained by the above disclosed treatment may be concentrated or evaporated, for instance, to atotal solids content of 20% to 50 %,without the objectionable deposition of any calcium phosphate. On storage, the concentrated whey will be found quite stable, and any precipitation of lactose that may eventually occur takes the form of a very fine precipitate that can be readily dispersed on agitation rather than the form of a coarse, grainy or sandy deposit.

The whey treated as described may also be spray dried, with or without previous concentration, to form a free flowing, stable, relatively non-hygroscopic powder that does not turn brown on storage and is extremely easily dispersible in water. Typical analyses of whey Dowders made from whey so treated are tabulated as follows:

No. Acid Lactose Protein Ash Total Per cent Per cent Per cent Per cent Per cent Per cent 8-1 l. 6 0. 2 84. 6 ll. 2 3. 3 100. 8 .5 8-3 5. 2 0. 7 80. 9 l1. 1 2. 2 100. 1 8-71 1. 6 0. 3 82. 8 l2. 1 2. 0 99. 4 S-l08.- 2. 8 0. 2 84. 6 11.0 1. 7 100. 3

As shown by thes data, the analyses all add to about Ordinary spray dried whey, when analyzed, does not give figures adding up to 100%, as indicated by the following table:

to be partially due to a modification of the lactose content during the concentrating or spray drying process.

The protein content of the spray dried whey of our invention diflers qualitatively from the.

protein content of ordinary spray dried whey. This difierence is illustrated by a series of parallel experiments with our novel spray dried whey and ordinary spray dried whey carried out by dispersing, as completely as possible, the spray dried wheys in water to make up dispersions containing 6.5% solids. The nitrogen contents of these dispersions were assayed before and after a filtration, with the results shown in the following table. Four samples of the filtered whey dispersions were treated, respectively, by adjusting the pH to 4.65; by adjusting the pH to 4.65 and heating to 100 C. for ten minute by incorporating 107 of trichloroacetic acid with the whey; in the whey to spray dried whey powder show some increase in weight due to adsorbed moisture for the first few days. After that time, the demineralized, de-

time required to reach this peak varied with the humidity.

and experimental data. surmised that Iated hereinbelow: the brown discoloration occurring on heat treat- Whey Demineralized whey Treatment N eon- Per cent N eou- Per cent tent, preeiptent, precipmEJcc. itated mgJcc. itatcd Whey not filtered 1. 19 1. 17 0 Whey filtered r e 1.17 0 1.18 0 Whey adjusted to pH 4.65, filtered 0. 96 18 0.78 34 Whey adjusted to pH 4.65, heated for min. at 100 0., flltercd. 0. 74 37 0. 54 54 Whey treated with 10% of trichloroacetic acid, filtered 0 40 66 0 28 76 Whey treated with sodium sulfate to one-half saturation and filtered 0 79 33 0. 79

were:

. Per cent Potassium nitrite 45 Sodium nitrite 66 Oxalic acid 76 Dibasic potassium phosphate 92 dried whey powder demineralized and deacidified to a 2% ash content. Each sample was weighed ment and/or storage of products is due to a and salts that might promote decomposition of proteins.

For a more positive correlation between amino acid content and extent of brown discoloration we employed f0rmol" tion" ardized alkali solution, titration.

with whey whey treated to the present invention, to eliminate according in results due to diiferenc'es in pH value variations .rather than to application of the methods of the present invention. Some samples were investigated without having been dried; others, after concentration and drying. The exact details are given hereinbelow.

We employed liquid whey having .a pH of 5.35

and containing 0.34% acid (as lactic). an aliquot acidifying media, as described hereinabove, ad-

justed to a pH of 6.75 with a small amount of decationized whey, and evaporated to dryness. This sample is referred to hereinbelow as sample No. 3. Two grams of each of these three whey powder samples were dispersed in 30 ml. of distilled water. The dispersions gave pH readings of 5.7 (sample No. 1), 6.7 (sample No. 2) and 6.6 (sample No. 3). The results of chemicalanalyses of the three samples are tabulated as follows:

Molstumper cent La 3' 1111 Protein 23 Ash 1514 Percent Percent Percent Percent No.1--- 5.1 4.2 3.5 121 60.8 0.00 3.3 No. 6.7 4.7 2.8 11.8 67.9 11.1 1.8 No.3 as :41 5.0 12.4 83.5 1.30 0.5

It will 'be noted that these analyses add up to 95.9% (sample No. l) 93.9% (sample No. 2), and 101.3% (sample No. 3).

-Two grams from each whey powder sample were wetted with 30 ml. distilled water in separate Petri dishes and placed in a chloroform oven for 1% days. At the end of this time there was very little browning. The dishes were then kept in another oven at 174 F. for 19 hoiirs. After removal from this oven, the samples'were dispersed in 30 ml. of water and filtered. The filtrates from samples Nos. 1 and2 were brown, but the filtrate from sample No. 3 was only slightly yellow.

The following table'shows the data obtained by determination of total nitrogen content and by "formor titration of these three whey samples before and after the. above described heat treatment:

transmission at various-wave lengths were light determined spectrophotometrically at various dilutions. The results are tabulated as follows:

Wave lengths in gamma: I

Sample Dilution asis 5.0 3.8 3.1 4.0 5.0 N01 1:5 11.5 15.0 25.0 38.2 53.0 1:10 28.8 38.2 61.0 63.8 75.2 1:20 55.0 53.5 13.2 82.1 88.5 No.2 1:10 11.24 23.5 33.2 41.8 01.0 N03 asis 6.20 5.2 7.0 11.0 18.9 15 31.0 40.5 51.2 52.5 122 Two grams of each whey powder sample were also wetted with 30 ml. distilled water and kept in an oven at 162 F. for 8 days. The whey powders were then dispersed in 30 ml. 0.1 normal sodium hydroxide. Spectrophotometric determinations of percentage of light transmission through dispersions of the various whey powders, before and after heating for 8 days at 162 F., and at various dilutions, are tabulated as follows:

Wave length in gammas Dilu- Semple Treatment an Unheated asis 41.5 48.5 54.0 03.0 13.0 No.1--- Heated asis 0.5 10.5 15.1 20.5 43.0 do 114 45.0 50.5 05.1 15.3 83.8 N02 0111154100..-. asis 40.2 43.1 50.0 64.8 15.1 LHeated 112 13.0 15.4 23.4 41.5 51.0 N03 unheated.-- 115i: .6.5 43.3 50.8 58.1 65.8 1155050 asis 10.0 20.2 348 43.0 53.1

nitrogenous matter determinable by The various data disclosed hereinabove show a definite reduction in browning even under extremely severe temperature conditions in the case of whey samples having a lowered content of formol" titration. This nitrogenous matter is ,believed to include principally amino acids, but may also include peptides and the like.

It will thus be seen that we products derived from whey and characterized by a smaller mineral, acid and decomposition product content than the starting material together with a substantially equal lactose content and a modified albumin content. These novel products can be heat treated without development of a stale or cooked flavor and have excellent keeping qualities. The demineralized, deacidifled whey of the present invention can be employed for blending with heat treated milk fat concentrates, such as cream, for the preparation of novel lacteal compositions described and claimed in our copending application entitled "Food product (filed of even date herewith).

have provided novel Unbeated Heated Sample 7 Per cent 01 Per cent of Formol Tr- Total Total Nitw Formol Ti- Total Total Nitrotration, ml. Nitrogen gen in Formol tration, ml. Nitrogen gen in Formol Titration Titration No. 1--- 2.55 an 0.51 1.20 1.01 4.10 No. 2 2. 58 3. 61 9. 81 1. Z) 1. 68 4. 57 No.3.-. 1.94 2.72. 7.03 1.35 1.89 4.88

Two grams of each whey powder sample were 70 also wetted with-30 ml. distilled water in separate Petri dishes and kept for 44 hours in an oven at F. The samples were then-dispersed in 30 ml. 0.1 normal sodium hydroxide. The resultant dispersions were filtered. and the percentages of 76 Many details of composition and procedure may be varied within a wide range without departing from the principles of this invention, and it is. therefore, not our purpose to limit the scope of this patent otherwise than necessitated by the scope of the appended claims.

We claim as our invention:

1. A method for the treatment of a liquid whey containing lactose, ash forming constituents, acid, milk protein and complex milk protein derivative decomposition products forming a part of the total assayable nitrogen of the material, the process serving to improve palatability and the ability of the material to withstand heat treatment without browning, the process comprising contacting the material with resinous cation and anion exchange mediums and thereby reducing the content of ash forming constituents of the material and the content of said decomposition products with an accompanying reduction in assayable total nitrogen, and thereby also modifying the protein content of the whey in such a manner that when the treated liquid whey is spray dried it forms a powder which is readily redispersible in water.

2. A method for the treatment of a liquid whey nitrogen of the material, the process serving to improve palatability and the ability of the material to withstand heat treatment without browning, the process comprising contacting the material with resinous cation and anion exwhich is greater than the like protein fraction of the same whey when dried before treatment. 3. A method for 10 panying reduction in assayable total nitrogen and thereby also modifying the whey, concentrating the resulting product to raise its total solids content to at least 20%, and drying the concentrated whey to produce a relatively stable, non-hygroscopic powder easily dispersible relatively stable, persed.

5. The method of making a stable product derived from liquid whey containing lactose, ash

REGINALD E. MEADE. PAUL n. CLARY, JR.

"REFERENCES crrnn The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,511,808 Grindrod Oct. 14, 1924 1,937,527 Otting Dec. 5, 1933 2,102,642 Otting Dec. 21, 1937 2,372,233 Thursto' Mar. 27, 1945 2,374,407 Block e a Apr. 24, 1945 2,404,367 Durant et al July 23, 1946 

